EP1287576A1 - Verfahren zum aufbringen einer festelektrolytschicht auf eine poröse elektrode - Google Patents
Verfahren zum aufbringen einer festelektrolytschicht auf eine poröse elektrodeInfo
- Publication number
- EP1287576A1 EP1287576A1 EP01943466A EP01943466A EP1287576A1 EP 1287576 A1 EP1287576 A1 EP 1287576A1 EP 01943466 A EP01943466 A EP 01943466A EP 01943466 A EP01943466 A EP 01943466A EP 1287576 A1 EP1287576 A1 EP 1287576A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- suspension
- solid
- hollow body
- layer
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
- H01M4/8626—Porous electrodes characterised by the form
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the invention relates to a method for applying a solid electrolyte layer to a porous electrode, in particular to an electrode for a solid ceramic fuel cell, in which a solid layer made of solid electrolyte material is applied to the electrode by separating solid parts from a suspension.
- a fuel cell regularly comprises an anode and a cathode, between which an electrolyte layer is applied.
- a fuel is passed over the anode surface and oxygen is passed over the cathode surface.
- An ion exchange takes place between the fuel and the oxygen via the electrolyte layer, so that a voltage develops between the anode and the cathode.
- the decisive factors for the efficiency of a fuel cell include the electrolyte layer, which on the one hand must be highly conductive for the ions and on the other hand should be largely impermeable to gases in order to prevent gas exchange between fuel and oxygen. High demands are therefore placed on the electrolyte layer.
- SOFC Solid Oxide Fuel Gell
- Solid electrolyte layer is arranged.
- Ceramic fuel cells with a planar geometry are known in which the anode and the cathode run essentially plane-parallel to one another.
- a cylindrical or tubular configuration is also known, in which the anode encloses the cylindrical cathode, including the solid electrolyte layer.
- elec- a variety of methods are known. From DE 196 09 418 C2, for example, it can be seen that a suspension is applied to a flat electrode, which contains solids from the solid electrolyte material. Excess solvent is removed by generating a negative pressure on the side of the porous electrode opposite the suspension.
- the suspension here has coarse and fine solids, the coarse solids initially clogging the pores of the electrode and ensuring a good connection between the electrolyte layer and the electrode.
- the fine parts then separate out on the coarse parts.
- the solid layer is dried and then sintered to form the solid electrolyte layer. This coating process is hardly suitable for non-flat surfaces, since it is the same
- the basic structure of a tubular fuel cell can be found in this document.
- the cathode this comprises a porous ceramic inner cylinder on which the electrolyte layer and then the anode as a jacket. brought.
- the anode of one fuel cell is connected directly to a so-called interconnector of the second fuel cell, the electrolyte layer and the anode of the fuel cells being interrupted in the area of the interconnector.
- both the electrolyte layer and the interconnector and the anode are usually applied by means of the EVD process.
- the article deals with the problem of replacing the expensive EVD process with other coating systems. While today, as suggested in the article, new coating processes for the interconnector and for the anode are developed and also used, the EVD process is still provided for the electrolyte layer in order to ensure a sufficiently high quality.
- the invention has for its object to provide a simple method for applying a solid electrolyte layer to a porous electrode, which is also suitable for complex geometries.
- a solid layer of solid electrolyte material is applied to the porous electrode, in particular to the electrode for a solid ceramic fuel cell, by separating solid parts from a suspension, the electrode being designed as a hollow body, which is immersed in the suspension to apply the solid layer.
- a pressure drop is set between the interior of the hollow body and the suspension, so that a solvent contained in the suspension reaches the interior.
- a major advantage of immersion in the suspension, especially in connection with the application of a vacuum, is that the solid particles are deposited uniformly on the outer surface, regardless of the special complex geometry of the hollow body, so that a thin, homogeneous solid electrolyte layer of constant thickness is formed in the end can.
- the pressure drop is preferably maintained via a suction line reaching into the interior in order to ensure a uniform separation of the solids content.
- the pressure drop or the pressure difference between the outside of the hollow body on the suspension side and the inside facing the interior is therefore kept as constant as possible during the entire deposition process.
- the solvent that has entered the interior is removed. This allows a constant pressure drop to be maintained in a comparatively simple manner and is favorable for a separation process of the solid particles that is as uniform as possible.
- the solvent is also removed via the suction line, so that a separate line system for the solvent is not required.
- the hollow body is removed from the suspension. So the suspension lies in excess and it is not necessary to adjust the amount of suspension in which the hollow body is immersed to the desired layer thickness.
- the pressure drop is preferably maintained when the hollow body is removed.
- Layer thickness of the already deposited solid layer the amount of solvent removed is used.
- the amount of separated solid particles can be derived from the amount of solvent removed. This allows easy determination of the layer thickness. Additionally or alternatively, the layer thickness is determined from the amount of suspension sucked in. The easiest way to do this is to measure or regulate the level of the suspension in a container in which the electrode is immersed.
- the suspension has coarse and fine solids contents, so that a high-quality solid electrolyte layer can form.
- the coarse solid particles settle in the pores of the hollow body and thus ensure a good connection of the electrolyte layer.
- the fine solids then separate out and ensure a largely dense formation of the electrolyte layer.
- the maximum diameter of the coarse solids content corresponds approximately to the maximum pore diameter of the hollow body.
- the values for this maximum diameter of the coarse solids fractions are typically between 5 and 20 ⁇ . With such a choice of diameter, it is prevented that coarse solids that are too large may cause unevenness on the surface and thus disadvantageous Lead to inhomogeneities. At the same time, a good formation of the electrolyte layer on the electrode is achieved.
- the proportion of the coarse solids content is preferably between about 1 and 15% by volume of the suspension. This proportion is sufficient to add the rough pores of the hollow body near the surface.
- the diameter of the fine solid particles corresponds to approximately 1/3 of the minimum pore diameter of the hollow body.
- the diameter is preferably approximately less than 1 ⁇ m, since the pore diameter of the smaller pores is approximately between 1 and 10 ⁇ m.
- a binder e.g. polyethyleneimine PEI
- PEI polyethyleneimine
- the solid layer is then preferably dried and compacted by sintering.
- the resulting layer is largely gas-tight.
- Sintering takes place, for example, in a conventional manner in a sintering furnace heated with heating elements at temperatures from 1300 ° C. to 1500 ° C. over a period of several hours.
- FIG. 1 shows a structure for carrying out the method
- FIG. 2 shows exemplary hollow body geometries
- FIG. 3 shows a diagram for the particle size distribution of the solid fractions in a suspension
- an arrangement for carrying out the method has a container 2 in which a suspension 4 is filled.
- the suspension 4 comprises a solvent L, fine solid fractions F and coarse solid fractions G and a binder B.
- the solid fractions F, G consist of a solid electrolyte material and are homogeneously distributed in the suspension 4.
- a cylindrical hollow body 6 is immersed in this suspension 4 and serves as an electrode, in particular a cathode, for a tubular fuel cell.
- the hollow body 6 consists of a porous ceramic.
- a suction line 12 is led into the interior 10 through the upper sealing plug 8A and extends within it up to approximately the opposite sealing plug 8B.
- the suction line 12 is connected to a pump device 14 and a flow measuring device 16 is arranged on it. This is connected to a control device 18, via which the pump device 14 can be controlled.
- the pump device 14 is used to generate a pressure gradient across the wall 20 of the hollow body 6. A pressure difference is therefore built up between the outside of the hollow body 6 facing the suspension 4 and the inside of the hollow body 6 oriented towards the interior 10.
- the pump device 14 is designed to separate gaseous components from liquid components. For this purpose, it has a discharge line 26 opening into a collecting container 28 and an exhaust gas line 30.
- the solid fractions F, G, B separate on the outside of the immersed hollow body 6 and form a solid layer 32 made of solid electrolyte material.
- the generation of the pressure difference via the pump device 14 ensures a continuous and permanent layer build-up. ⁇ on the porous formation of the hollow body 6 reason, the solvent L passes through the hollow body 6 into the inner C ⁇ co M ) F>
- the diameter is typically between 1 and 10 ⁇ m, for example.
Landscapes
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Chemical & Material Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Secondary Cells (AREA)
Abstract
Description
Claims
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP01943466.1A EP1287576B1 (de) | 2000-06-09 | 2001-06-01 | Verfahren zum aufbringen einer festelektrolytschicht auf eine poröse elektrode |
| CY20161100227T CY1117289T1 (el) | 2000-06-09 | 2016-03-17 | Μεθοδος για την εφαρμογη μιας στερεης ηλεκτρολυτικης στρωσης σε ενα πορωδες ηλεκτροδιο |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP00112393 | 2000-06-09 | ||
| EP00112393 | 2000-06-09 | ||
| EP01943466.1A EP1287576B1 (de) | 2000-06-09 | 2001-06-01 | Verfahren zum aufbringen einer festelektrolytschicht auf eine poröse elektrode |
| PCT/EP2001/006251 WO2001095420A1 (de) | 2000-06-09 | 2001-06-01 | Verfahren zum aufbringen einer festelektrolytschicht auf eine poröse elektrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1287576A1 true EP1287576A1 (de) | 2003-03-05 |
| EP1287576B1 EP1287576B1 (de) | 2015-12-23 |
Family
ID=8168949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP01943466.1A Expired - Lifetime EP1287576B1 (de) | 2000-06-09 | 2001-06-01 | Verfahren zum aufbringen einer festelektrolytschicht auf eine poröse elektrode |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1287576B1 (de) |
| AU (2) | AU2001266040B2 (de) |
| CA (1) | CA2411711C (de) |
| CY (1) | CY1117289T1 (de) |
| DK (1) | DK1287576T3 (de) |
| ES (1) | ES2557739T3 (de) |
| NO (1) | NO328244B1 (de) |
| PT (1) | PT1287576E (de) |
| WO (1) | WO2001095420A1 (de) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL9002168A (nl) * | 1990-10-05 | 1992-05-06 | Blandikus Catharikus Jaspers E | Holle elektrode voor een elektrochemische cel voorzien van ten minste een toe- en een afvoeropening voor gassen, alsmede elektrochemische cel die een dergelijke elektrode omvat. |
| DE19609418C2 (de) * | 1996-03-11 | 1998-08-13 | Forschungszentrum Juelich Gmbh | Beschichtung von porösen Elektroden mit dünnen Elektrolytschichten |
| DE19628593A1 (de) * | 1996-07-16 | 1998-01-22 | Hans Hoffmann | Elektrodenanordnung, daraus hergestellte Brennstoffzelle und Verfahren zu deren Herstellung |
-
2001
- 2001-06-01 CA CA2411711A patent/CA2411711C/en not_active Expired - Fee Related
- 2001-06-01 EP EP01943466.1A patent/EP1287576B1/de not_active Expired - Lifetime
- 2001-06-01 WO PCT/EP2001/006251 patent/WO2001095420A1/de not_active Ceased
- 2001-06-01 AU AU2001266040A patent/AU2001266040B2/en not_active Ceased
- 2001-06-01 DK DK01943466.1T patent/DK1287576T3/en active
- 2001-06-01 PT PT1943466T patent/PT1287576E/pt unknown
- 2001-06-01 ES ES01943466.1T patent/ES2557739T3/es not_active Expired - Lifetime
- 2001-06-01 AU AU6604001A patent/AU6604001A/xx active Pending
-
2002
- 2002-12-04 NO NO20025826A patent/NO328244B1/no not_active IP Right Cessation
-
2016
- 2016-03-17 CY CY20161100227T patent/CY1117289T1/el unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO0195420A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001095420A1 (de) | 2001-12-13 |
| CA2411711A1 (en) | 2001-12-13 |
| ES2557739T3 (es) | 2016-01-28 |
| AU2001266040B2 (en) | 2006-03-16 |
| DK1287576T3 (en) | 2016-01-25 |
| CY1117289T1 (el) | 2017-04-26 |
| EP1287576B1 (de) | 2015-12-23 |
| NO328244B1 (no) | 2010-01-18 |
| NO20025826L (no) | 2003-02-06 |
| AU6604001A (en) | 2001-12-17 |
| CA2411711C (en) | 2010-11-30 |
| PT1287576E (pt) | 2016-03-03 |
| NO20025826D0 (no) | 2002-12-04 |
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